Oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol aldehyde resins, and method of making same



OXYALKYLATED POLYEPOXIDE TREATED AMlNE-MODIFIED THERMOPLASTIC PHE- NOL ALDEHYDE RESINS, AND METHOD OF MAKING SAIWE Melvin De Groote, St. Louis, and Kwan-ting Siren, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del, a corporation of Delaware No Drawing. Original application June 26, 1953, Serial No. 364,503, now Patent No. 2,771,427, dated November 20, 1956. Divided and this application September 11, 1956, Serial No. 609,098

4 Claims. (Cl. 260-45) The present invention is a continuation-inpart of our copending application, Serial No. 338,575, filed February 24, 1953, now U.S. Patent 2,771,437, and a division of our copending application Serial No. 364,503, filed June 26,

1953, now U.S. Patent 2,771,427.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing,

breaking or resolving emulsions of the Water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The present invention is concerned with a three-step manufacturing process involving 1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic non-hydroxylated polyamines, herein after described in detail, and formaldehyde; (2) oxyalkylated of the condensation product with certain phenolic polyepoxides hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain monoepoxides, also hereinafter described 4 in detail.

For a number of reasons it is usually most desirable to use the diepoxide type of polyepoxide. In preparing diepoxides or the low molal polymers one usually obtains cogeneric materialswhich may include monoepoxides. However, the cogeneric mixture is invariably characterized by the fact that there is on the average, based on the molecular weight, of course, more than one epoxide group per molecule.

A more limited aspect of the present invention is represented by the products wherein the polyepoxide is represented by (1) compounds of the following formula:

and (2) cogenerically associated compounds formed in the preparation of (1) preceding, with the proviso that it consists principally of the monomer as distinguished from other cogeners.

Notwithstanding the fact that subsequent data will be clei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i.e., divalent linking radicals. Our preference is that either diphenyl compounds 30 in which R represents a divalent radical selected from the 2,388,429 Patented May 26, 1959 be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

If it were not for the expense involved in preparing and purifying the monomer we would prefer it to any other form, i.e., in preference to the polymer of mixture of polymer and monomer.

Stated another way, We would prefer to use materials of the kind described, for example, in US. Patent No. 2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula wherein R is an aliphatic hydrocarbon bridge, each n independently has one of the values 0 and 1, and. X is an alkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings and employed for combination with the reactive amine-modified phenolaldehyde resin condensates as herein described are characterized by the following formula and cogenerically associated compounds formed in their preparation:

class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydric oxygen atom, the divalent radical the divalent O H radical, the divalent sulfone radical, and the divalent monosulfide radical -S, the divalent radical CH SCH and the divalent disulfide radical SS; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol 5 in which R, R, and R' represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer including zero and l and n represents a whole number not greater than 3. The above mentioned compounds and those cogenerically associated cornpounds formed in their preparation are thermoplastic and organic solvent-soluble. Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in anorganic solvent means any of the usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible.v Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the amine resin condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i.e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2- 3,4 diepoxybutane).

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i.e., the compound having 2 oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of 2 moles of the amine condensate to one mole of the oxyalkylating agent desirable to add a small amount of acetone to the xylenemethanol mixture, for instance, 5% to of acetone.

A mere examination of the nature of the products before and after treatment with the polyepoxide reveals that the polyepoxide by and large introduces increased hydrophobe character or, inversely, causes a decrease in hydrophile character. However, the solubility characteristics of the final product, i.e., the product obtained by oxyalkylation of a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, while propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in solubility characteristics or in the hydrophile-hydrophobe character so as to be about the same as prior to oxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtained in the manner described are, in turn, oxyalkylationsusceptible and valuable derivatives can be obtained by further reaction with other alkylene oxides, for instance, styrene (phenyl ethylene oxide), cyclohexyl ethylene oxide, ethylene imine, propylene imine, acrylonitrile, etc.

Similarly, the oxyalkylated polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a l,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U.S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing ingives aproduct which may be indicated as follows: dustries; as wetting agents and detergents in the acid H H I H H:C--C-C OR [R],.-R1OOC--C --OR -[R].R 0-C-C--GH,

H; H H: H: l

(condensate) (condensate in which the various characters have their previous significance and the characterization condensate is simply an abbrevation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form which is the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances Where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve them a mixture of xylene and methanol, for instance, 80 parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i.e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufiiciently hydrophile character to at least meet the test set forth in U.S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into ten parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned With our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with basic nonhydroxylated polyamines having at least one secondary amino group and having not over 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, and substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previiously prepared amine modified phenol aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 7, preceding, i.e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously'described chemical compounds or reaction products; and

Part 10 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solvent-soluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinpolyepoxides in the form of dithe monomer. Certain monomers have been preparedand described in the literature and will be referred to subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, We have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a Ivariety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, andthe materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers are satisfactory. The formula for this compound is H H H 1 H H H \O/ CH: 0

Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the

text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived at column 7, line 21.

PART 3 Subdivision A from the other groups illustrated for the reason that nothing more than mere substitution of one compound The preparations of the diepoxy derivatives of the difor the other would be required. Thus, what is said phenols, which are sometimes referred to as d1glyc1dyl hereinafter, although directed to oneclass or a few classes, e hers, have een dcscrlbcd 1n a number of patents. For applies with equal force and effect to the other classes convemence, reference Wlll be made to two only, to wt, of epoxide reactants, aforementioned U.S. Patent 2,506,486, and aforemen- If sulfur-containing compounds are prepared they h n Pfifcnt P- Q, should be freed from impurities with considerable care Purely by way of lllustratlon, the followmg diepoxldes, for the reason that any time that a low-molal sulfuror dig y y ethefs as QY are 0met1mes termed, are containing compound can react with epichlorohydrin there included for purpose of illustration. These particular may be formed a by-product in which the chlorine hapcompounds are described in the tWO patents 111st menpened to be particularly reactive and may represent a honed.

TABLE I Ex- Patent ample Dlphenol Dlglyoldyl ether refernumber enc/e 011400214011), Di(epoxyprop0xyphenybmothane 2, 506,486 HSCHKJuHAOHh. Dl(epoxypropoxyphenyl)rnethylmethane.. 2, 506, 4 (CH3)2C(O0H4O Dl(epoxypropoxypheuyl)dimethylmethana. 2,506,435 CnH5C(CH3) (Gui-140E); Di(epoxypropoxyphenyl)ethylmethylmethane. 2, 505, 4 s (C1115) 2O (OgHtOFDz. Dl(epoxy,propoxyphenyl) diethylmeth ane 2, 506, 43 CH;O(C;H (C H 0H Di(epoxypropoxyphenybmethylpropylmethane.. 2, 501;, 4st, OH3C(COH5)(CBH4OH) Di(epoxypropoxwphenyl)methylphenylmethane 2, 506,480 0211;0(G5H XC HH) Di(epoxyprop0xyp eny)ethy1phenylmethane 2,506,436 C3H C(C1-,H,-,)(C H4OH) Di(epoxypropoxyphenyl)propylphenylmethane 2, 506, 48G 0.300(0 11, 11 0 Di(epoxypropoxyphenyl)butylphenylmethan 2,506,4 5 (CH C H )OH(C Di(e orypropoxyphenyl)tolylmethane. 2, 506, 480 (011109110001 5 Di(erqoxyp p ryp v ly 2,506,481 Dihydroxy diphenyl 4,4-b1s(2,3-epoxyprop0xy)dlphenyl 2, 530, 353 (CH3)C(C4H5.G5H3OH)2 2,2-bis(4-(2,3-epoxypropoxy)2-tert1arybutylphenyl))propane 2, 530,353

product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 H: H H:

PART 3 Subdivision B As to the preparation of low-molal polymeric epoxides or mixtures reference is made to numerous patents and particularly the aforementioned U. S. Patents Nos. 2,575,- 558 and 2,582,985.

In light of aforementioned U.S. Patent No. 2,575,558, the following examples can be specified by reference to the formula therein provided one still bears in mind it is in essence an over-simplification.

TABLE II (in which the characters have their previous significance) Example -R1O from HR10H --R n n Remarks number B1 Hydroxy benzene CH: 1 0, 1, 2 Phenol known as bis-phenol A. Low I polymeric mixture about 96 or more -C- where n'=0, remainder largely where I n'=1, some where n'=2. CH:

B2 ..do CH; 1 0, 1, 2 Phenol known as bis-phenol B. See note I regarding B1 above. a CH:

B3 Orthobutylphenol CH: 1 0,1, 2 Even though at is preferably 0, yet the l usual reaction product might well con- -0 tam materials where n is 1, or to a lesser degree 2. CH;

B4 Orthoamylphenol OH: 1 0,1,2 Do.

Orthooctylphanoh. CH; 1 0,1,2 Do.-

TABLE II-Contlnued Example moirom HR OH R- n Remarks number B6........ Orthononylphenol CH: 0, 1,2 Even though 1: is preferably (1, yet the I usual reaction product might well-con C- tain materials where n 1s 1, or to a 5 lesser degree 2. y

B7 Orthododecylphenol; (13H: 0, 1, 2 Do.

CH: I B8 Metacresol OH; 0,1, 2 See prlor note. This phenol used as I initial material is known as bis-phenol C- For other suitable bis-phenols see I U. S. Patent 2,564,191. CH:

39 ..do CH: 0, 1, 2 See prior note.

111: CH: 1310 Dlbntyl (ortho-para) phenol- ICE}! 0,1,2 Do.

B11 Dlamyl (ortho-para) phenol. lg 0,1,2 Do.

B12.-.- Dloetyl (ortho-para) phenol. 0,1,2 Do.

B13 Dlnonyl (ortho-para) phenol. g 0, 1,2 Do.

1314...... Dlamyl (ortho-para) phenol. 13 0,1, 2 Do.

I CH3 B15 ..do 1g 0, 1, 2 Do;

1816...... Hydroxy benzene Z 0,1,2 Do;

B17 Diamyl phenol (ortho-para). SS 0, 1, 2 Do;

B18 .do -S 0, 1, 2 D0. B19 Dlbutyl phenol (ortho-pera). lg 13 0,1, 2 Do,

B20 -do H H 0, 1, 2 Do.-

C C. H H

B21 Dlnonylphenol (ortho-para) 15 g 0,1, 2 Do.

A H H 1322.--... Hydroxy benzene 0,1,2 Do,

B23 do None 0,1,2 Do.-

B24 Ortho-lsopropyl phenol OH; 0, 1, 2 See prior note. (As to preparation 014,4- 1 isopropylidene bis-(2-isopropylphenol) C see U. 8. Patent No. 2,482,748, dated I Sept. 27, 1949, to Dietzler.) 1 l CH:

B25 Para-octyl phenol CHaS-CHa 0, 1, 2 See prior note. (As to preparation of the phenol sulfide see U 8. Patent No. 2,488,134, dated NOV. 15, 1949, to Mikeska et a1.) I B26. Hydroxybenzene..-. CH: 0, 1, 2 See prior note. (As to'preparation or the phenol sulfide see U. S. Patent;v No. I; 2,526,545.)

11 Subdivision C The prior examples have been limited largely to those in which there is no divalent radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

J; in.

HO OH CH; CH; wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U.S. Patent No. 2,515,907.

(0 4)o 2 t )I in which the C H groups are secondary amyl groups. See U.S. Patent No. 2,504,064.

HO OH 60 See U.S. Patent No. 2,285,563.

H OH, H

CH -C See U.S. Patent No. 2,503,196.

12 HO OH H, t t

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U.S. Patent No. 2,526,545.

OH OH CH; CH;

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U.S. Patent No. 2,515,906.

CH=CH See U.S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

s u s n such as Alkyl Al kyl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U.S. Patent No. 2,430,002.

See also U.S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH CH1 OH; OH

R1 R1 R1 R2 in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is l to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfides, and polysulfides.

PART 4 In the above formula n represents a small whole number varying from 1 to 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i.e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of US. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned US. Patent No. 2,499,365, or in US. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated-organic solventsoluble, water-insoluble, low-stage phenolaldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylolforming reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at least 4 carbon atoms and not more than 24 carbon atoms, and substituted in the 2,4,6 position.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated polyamine as specifiedfi following the same idealized over-simplification previously re- In conducting reactions of this kind one does not necessarily obtain ahundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the'resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

011 OH OH R H H H o o ON/ H Hi H \R, R R

on OH OH on 0H 0 E n H H n o o 0 o I- 0 H H H H H R R n R R R n R As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

OH OH U WU M I in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned US. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a catalyst, having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more-rapidly in the presence of a small amount of a freebase. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polyferred to, the resultant product might be'illustrated thus: mer, i.e., one having just 3 units, or just 4 units, or

The basic nonhydroxylated amine may be designated just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the followlng table:

TABLE 111 M01. Wt. Ex- Position R of resin ample R of R derived n molecule number from (based on n+2) Tertiary butyl Para 3. 5 882. 5 Secondary butyl.- rtl1o 3. 882. 5 Tertiary amyl Para..." 3. 5 959. 5 Mixed secondary Ortho.-- 3. 5 805. 5

and tertiary my].

Tertiary 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 Nonyl 3. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1,148. 5 onyl o 3. 5 1, 456. 5 Tertiary butyl Propional- 3. 5 1, 008. 5

dehyde.

Tertiary amy] .d0 3. 5 l, 085. 5 Nony do 3. 5 1, 393. 5 Tertiary butyL 4. 2 996. 6

PART 5 As has been pointed out, the amine herein employed as a reactant is a basic secondary polyamine and preferably a strongly basic secondary polyamine free from hydroxyl groups, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character.

Previous reference'has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i.e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. By way of example the following formulas are included. It will be noted they include some polyamines which, instead of being obtained from dichloride, propylene dichloride, or

16 the like, are obtained from dichloroethyl ethers in which the divalent radical hasa carbon atom chain interrupted by an oxygen atom:

NC H4NCgHN H H H Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylating agent of the kind described, for example, dimethylsulfate; or else a reaction which involves an alkylene oxide, such as ethylene oxide or propylene oxide, followed by the use of an alkylating agent or the comparable procedure in which a halide is used.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary aralkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylating agent, such as dimethyl sulfate. In a somewhat similar procedure the secondary amine of the kind just specified can be reacted with an alkylene oxide such as ethylene oxide, propylene oxide, or the like, and then reacted with an imine followed by the final step noted above in order to convert the primary amino group into a secondary amino group.

Reactions involving the same two classes of reactants previously described, i.e., a secondary amine plus an imine plus an alkylating agent, or a secondary amine plus an alkylene oxide plus an imine plus an alkylating agent, can be applied to another class of primary amines which are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula:

Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by as described in US. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in US. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyarnines are the kind described in British Patent No. 456,517 and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as similar. This is illustrated by reference to two prior examples:

CH3 CH3 H propyleneNpropyleneN H H In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as differentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two different structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained '18 due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

CH CH Over and above the specific examples which have appeared previously, attention is directed to the fact that added suitable polyamines are shown in subsequent Table II.

PART 6 I The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, al-"" though it may be so illustrated in an idealized simplifi cation, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-aminealdehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain aheatreactive resin. are not heat-convertable and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot ofthe kind described in aforementioned US. Patent No. 2,499,368; In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; infact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble' except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solvent such as dioxane or the diethylether of ethylene glycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to usean initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more diflicult perhaps to add a solid material instead of the liquid solution, and, everything else being equal, the latter is apt to be more economical.

Since the condensation products obtained '19 In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction Where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain without complete removal. Even if one starts with a resin which is almost water-white in color, the products obtained are almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solventfree basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicles such as a dilute solution, for instance, a solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i.e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylationl, and the third factor is this, (0) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the Water-soluble unreacted formaldehyde, if any, or a Water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reactionan opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. I have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U.S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three phase system instead of a twophase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the most, up to 10-24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyaminc or formaldehyde. At a higher temperature We use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the Water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 21 C., and generally slightly above 100 C. and below 150 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is 22 until solution was complet It was then adjusted to approximately 30" to 35 C. and 176 grams of symmetrical dimethylethylene diamine added. The mixture was stirred vigorously and formaldehyde added slowly.

eliminated, is continued until the reaction mass is homo- In this particular instance the formaldehyde used was geneous and then for one to three hours longer. The rea 30% solution and 200 grams were employed which moval of the solvents is conducted in a conventional Were added in a little short of 3 hours. The mixture was manner in the same way as the removal of solvents in stirred vigorously and kept within a temperature range resin manufacture as described in aforementioned US. of 30 to 46 for about 19 hours. At the end of this Patent No. 2,499,368. time it was refluxed, using a phase-separating trap and Needless to say, as far as the ratio of reactants goes a-small amount of aqueous distillate withdrawn from time we have invariably employed approximately one mole of to time. The presence of unreacted formaldehyde was the resin based on the molecular weight of the resin noted. Any unreacted formaldehyde seemed to disapmolecule, 2 moles of the secondary polyamine and 2 pear within approximately two to three hours after remoles of formaldehyde. In some instances we have fluxing started. As soon as the odor of formaldehyde added a trace of caustic as an added catalyst but have was no longer detectible the phase-separating trap was found no particular advantage in this. In other cases set so as to eliminate all the water of solution and rewe have used a slight excess of formaldehyde and, again, action. After the water was eliminated part of the xylene have not found any particular advantage in this. In other was removed until the temperature reached approxicases we have used a slight excess of amine and, again, m ly or ig ly gh The mass Was kept have not found any particular advantage in so doing. at this higher temperature for three tofou-r hours and re- Whenever feasible we have checked the completeness of action stopped. During this time, any additional water reaction in the usual ways, including the amount of water which was probably water of reaction which had formed, of reaction, molecular weight, and particularly in some was eliminated by means of the trap. The residual xylene instances have checked whether or not the end-product was permitted to stay in the cogeneric mixture. A small showed surface-activity, particularly in a dilute acetic amount of the sample was heated on a water bath to reacid solution. The nitrogen content after removal of move the excess xylene and the residual material was unreacted polyamine, if any is present, is another index. dark red in color and had the consistency of a sticky In light of what has been said previously, little more fluid or tacky resin. The overall time for reaction was need be Sa1d as to the 301113} procedure p y f somewhat less than 30 hours. In other examples, it varthe preparation of the herein desc r1bed condensation i f a li over 2 hours up to 36 hours The P The followmg example W111 serve by Way of time can be reduced by cutting the low temperature Illustrauon: E 1 1b period to approximately 3 to 6 hours.

xamp e Note that in Table IV following there are a large The phenol-aldehyde resin is the one that has been number of added examples illustrating the same proidentified previously as Example 1a. It was obtained cedure. In each case the initial mixture was stirred and from a para-tertiary butylphenol and formaldehyde. The held at a fairly low temperature (30 to C.) for a resin was prepared using an acid catalyst which was comperiod of several hours. Then refluxing was employed pletely neutralized at the end of the reaction. The 4 until the odor of formaldehyde disappeared. After the molecular weight of the resin was 882.5. This correodor of formaldehyde disappeared the phase-separating sponded to an average of about 3% phenolic nuclei, as trap was employed to separate out all the water, both the value for n which excludes the 2 external nuclei, the solution and condensation. After all the water had i.e., the resin was largely a mixture having 3 nuclei and been separated enough xylene was taken out to have the 4 nuclei, excluding the 2 external nuclei, or 5 and 6 final product reflux for several hours somewhere in the overall nuclei. The resin so obtained in a neutral state range of 145 to 150 C., or thereabouts. Usually the had a light amber color. mixture yielded a clear solution by the time the bulk of 882 grams of the resin identified as In preceding were the water, or all of the water, had been removed. powdered and mixed with a somewhat lesser weight of Note that as pointed out previously, this procedure is xylene, i.e., 600 grams. The mixture was refluxed illustrated by 24 examplesinTable IV.

TABLE IV Strength of Reac- Reac- Max. Ex. Resin Amt Amine used and amount formalde- Solvent used tion tion distill No. used grs. hyde soln. and amt. temp., time, temp,

and amt. 0. hrs. C.

882 AmineA1762 30%200g Xylene600g. 20-23 26 152 480 AmineASS 30g, g Xylene450g 20-21 24 150 633 AmiueA88g 30 01002--- Xylene550g.- 20-22 28 151 441 AmineB 116 37% 81g- Xylene400g 20-28 36 144 480 AmineBllfiz 37%81g. Xylene450g 22-30 25 156 633 AmlneB 116! 37% 81g- Xylene 600g 21-28 32 150 882 Amine0204 30%200g Xylene600g.. 21-23 30 480 Amine0102g 37% 100g.- Xylene450g. 20-25 35 148 633 AmineClOZg 37%100g-- Xylene 500 g 20-27 35 143 473 AmineD 117 2 -1- 37% 81g Xy1ene425g 20-22 31 145 511 AmineD1172 37%81g Xylene 500g. 24 146 665 AmineD117 36 151 441 AmineE1582 1 32 480 AmineE158z g 30 152 595 AminoE1582 g Xylene 550 g 21-26 27 145 441 AmineFlQIg 30% 100g Xylene400g 20-23 25 141 480 AmineI 191g Xy1ene400 g 22-27 29 143 511 AmineFlQla Xy1ene450g.. 23-25 36 149 498 AmineF191g Xylene450g... 21-26 32 148 542 AmineGl74 Xylene 500 g.- 21-23 30 148 547 AmineG1742 30%100g Xylene 500g 20-26 36 152 1a 441 AmineG174z 30%100g Xy1ene440g 21-24 32 150 231)---- 248.--- 595 AmineH2S2 37% 81 Xylene500g.. 21-28 25 150 24b 252.--- 391 AmineHMlz 30% 50g Xy1ene350g. 21-22 28 151 23 As to the formulas of the above amines referred to as Amine A through Amine H, inclusive, see immediately below:

The products obtained as herein described by reactions involving amine condensates and diglycidyl ethers or the equivalent are valuable for use as such. This is pointed out in detail elsewhere. However, in many instances the derivatives obtained by oxyalkylation are even more valuable and from such standpoint the herein described products may be considered as valuable intermediates. Subsequent oxyalkylation involves the use of ethylene oxide, propylene oxide, butylene oxide, glycide, etc. Such oxyalkylating agents are monoepoxides as differentiated from polyepoxides.

It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may require a pressure vessel as in the case of ethylene oxide, it is convenient to use the same reaction vessel in both instances. In other words, the 2 moles of the aminemodified phenol-aldehyde resin condensate would be reacted with a polyepoxide and then subsequently with a monoepoxide. In any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, US. Patent No. 2,499,365.

Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chloride.

Furthermore, insoluble catalysts such as clays or specially 7 prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i.e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve. If the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one which is not oxyalkylationsusceptible. It is easy enough to select a suitable solvent if required in any instance but, everything else being equal, the solvent chosen should be the most economical one.

Example 1C The product was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained from resin 3a. Resin 3a was obtained from tertiary amylphenol and formaldehyde. Condensate 2b employed as reactants resin 3a and the amine designated as Amine A at the end of Table IV which is symmetrical dimethyl ethylenediamine. The amount of resin employed was 882 grams; the amount of symmetrical dimethyl ethylenediamine employed was 176 grams; and the amount of 30% formaldehyde employed was 200 grams. The amount of solvent was approximately 600 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples are characterized by the fact that no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of a diepoxide.

In any event, 116 grams of the condensate dissolved in approximately 116 grams of xylene were stirred and heated to C. 17 grams of the diepoxide previously identified as 3A and dissolved in an equal weight of xylene were added dropwise. An initial addition of the xylene solution carried the temperature to 109 C. The remainder of diepoxide was added in approximately one hours time. During this period the temperature rose to about 118 C. The product was allowed to reflux at a temperature of about 128 C. using a phase-separating trap. A small amount of xylene was removed by means of the phase-separating trap so the refluxing temperature rose to a maximum of C. The mixture was then refluxed at 160 C. for about 6 hours until the reaction stopped and the xylene which had been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in order to examine the physical properties. The material was a dark red viscous semisolid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20% methanol.

. However, if the material was dissolved in an oxygenated solvent and then shaken with gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addimoles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like.

tion of a little acetone. 5 In some instances an oxygenated solvent, such as the The procedure employed of course is simple in light diethyl ether of ethyleneglycol may be employed. Anof what has been said previously and in effect is a proceother procedure which is helpful is to reduce the amount dure similar to that employedin the use of glycide or of catalyst used, or reduce the temperature of reaction by methylglycide as oxyalkylating agents. See, for example, adding a small amount of initially lower boiling solvent Part 1' of US. Patent No. 2,602,062, dated July 1, 1952, such as benzene, or use benzene entirely. Also, we have to De Groote. found it desirable at times to use slightly less than appar- Various examples obtained in substantially the same ently the theoretical amount of diepoxide, for instance, manner are enumerated in the following tables: to instead of The reason for this fact TABLE V (Jon- Diep- Time Max. Ex. den- Amt, oxide Amt., Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used hrs.

116 3A 17 133 21 6 160 Dark semi-solid. 122 3A 17 139 211 7 165 Do. ,111 3A 17 128 2:1 6 162 Do. 119 3A 17 136 2:1 6 170 Do. 8A 17 137 211 6 160 Do. 159 3A 17 176 2:1 8 168 Dark solid mass. 122 3A 17 139 2:1 7 165 Do. 143 3A 17 160 21 s 170 Do. 3A 17 157 21 s 162 Do. 146 32. 17 168 211 s 165 D0.

s substantially similar to that which was described in Example 10.

TABLE VI g A t X fi? A c x 1 M 1 firms t Ex. enin 0 e m y ene, 0 a! 0 reacem N0. sate grs 1 used grs. gm ratio on, o g Color and physical state used 116 B1 27. 5 143. 5 2:1- 7 162 Dark semi-solid. 122 B1 27. 5 149. 5 2:1 6 165 D0. 111 B1 27. 5 138. 5 2: 1 7 D0. 119 B1 27. 5 146. 5 2:1 8 Do. 120 B1 27. 5 147. 5 2: 1 8 168 D0. 159 B1 27. 6 186. 5 2:1 8 160 Dark solid mass. 122 B1 27. 5 149. 5 2:1 7 160 D0. 143 B1 27. 5 170. 5 2: 1 8 162 D0. 140 B1 27. 5 167. 5 2:1 8 160 D0. 146 B1 27. 5 173. 5 2:1 8 165 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per moleeule TABLE VIII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. N o. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-hnking or gelling even when the molal ratio in the order of 2 may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight 'by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin) CH (Amine) in which D.G.E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case 03 a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CH: (Amine)] [D. G.E.]

[(Amine) CH2 (Amine) [(ReSlI1)CHa(RESi11)] [D.G.E.] [(Resin) CHr(Resin) 2?. [(Amine) CH (Amine)]\ [D G.E

[(Resin)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 The preparation of the compounds or products described in Part 7, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal difference is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, i.e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. In the oxyalkylations carried out to produce compositions used in accordance with the present application, conventional equipment, i.e., a stainless steel autoclave suitably equipped, and conventionally oxyalkylation conditions were used.

The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of the polyepoxide treated amine-modified phenol-aldehyde condensation product.

Example 1E The polyepoxide derived oxyalkylation susceptible compound employed is the one previously designated and described as Example 1D. Polyepoxide-derived condensate 1D was obtained, in turn, from condensate 2b and diepoxide Bl. Reference to Table IV shows the composition of condensate 2b. Table IV shows it was obtained from Resin 5a, Amine A and formaldehyde. Amine A is symmetrical dimethyl ethylene diamine. Table III shows that Resin 5a was obtained from parasubstituted tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-susceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated as a separate item. To be consistent, of course, the oxyalkylation-susceptible compound abbreviated as OSC is indicated on a solvent-free basis.

14.35 pounds of the polyepoxide-derived condensate were mixed with 14.35 pounds of solvent (xylene in this series) along with one pound of finely powdered caustic soda as a catalyst. This reaction mixture was treated with 14.25 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 65.0 and the theoretical molecular weight was approximately 5,700.

Adjustment was made in the autoclave to operate at a temperature of 125 to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the ethylene oxide in approximately one-half hour and then continued stirring for hour longer simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide could have been purpose of making some tests on various oil field emul-.

sions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables IX, X and XI.

The size of the autoclave employed was 35 gallons. In innumerable oxyalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a difierent oxide.

Example 2E This example simply illustrates further oxyalkylation of Example 1E, preceding. The oxyalkylation-susceptible compound, to wit, Example 1D, is the same one as was used in Example 1E, preceding, because it is merely a continuation. In the subsequent tables, such as Table IX, the oxyalkylation-susceptible compound in the horizontal line concerned with Example 2E refers to oxyalkylation-susceptible compound, Example 1D. Actually one could refer just as properly to Example 1E at this stage. It is immaterial which designation is used so long as it is understood and such practice is used consistently throughout the tables. The amount of oxide introduced in the subsequent steps was less than in the initial stage. -The amount introduced in the second step was 4.75 pounds. This means the amount of oxide at the end was 19.0 pounds. It is meant that the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 96 to 1. The theoretical molecular weight was almost 6,650. There was no added solvent. In other words, it remained the same, that is, 14.35 pounds, and there was no added catalyst. The entire procedure was substantially the same as in Example 1E, preceding.

In all succeeding examples the time and pressure were the same as previously, to wit, to C., and the pressure 10 to 15 pounds. The time element was hour, the same as before.

Example 3E The oxyethylation proceeded in the same manner as described in Example 1E and 2E. There was no added solvent and no added catalyst. The oxide added was 4.75 pounds. The total oxide at the end of the oxyalkylation procedure was 23.75 pounds. The molal ratio of oxide to condensate was 128 to l. The theoretical molecular weight was approximately 7,620. As previously noted, condtions in regard to temperature and pressure were the same as in Examples 1E and 2E. The time period was one hour.

Example 4E The oxyethylation was continued and the amount of oxide added was the same as before, to wit, 4.75 pounds. The amount of oxide added at the end of the reaction was 28.50 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was the same as before, to wit, one hour. The reaction at this point showed some tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was about to 1 and the theoretical molecular weight was 8,600.

29 Example E The oxyalkylation was continued with the introduction of another 9.50 pounds of oxide. No added solvent was introduced, and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the mac tion was approximately 10,500. The molal ratio of oxide to oxyalkylation-susceptible compound was 195 to 1. The time period was 1 /2 hours.

Example 6E The same procedure was followed as in the previous examples without addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 19.00 pounds. The time required to complete the reaction was two hours. At the end of the reaction the ratio of oxide to oxyalkylation-susceptible compound was approxmately 320 to 1, and the theoretical molecular weight was about 14,250.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables IX through XIV, inclusive.

In substantially every case a SS-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables IX, X and XI, it will be noted that compounds 1E through 18E were obtained by the use of ethylene oxide, whereas Examples 19E through 36E were obtained by the use of propylene oxide; and Examples 37E through 54E were obtained by the use of butylene oxide.

Referring now to Table X specifically, it will be noted that the series of examples beginning with 1F were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 1E as the oxyalkylation-susceptible compound in the first six examples. This applies to series 1F through 18F.

Similarly, series 19F through 36F involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19F was prepared from 23E, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 37F through 54F involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55F through 72F, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73F through 90F involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1G through 186 the three oxides were used. It will be noted in Example 1G the initial compound was 76F; Example 76F, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1G through 6G was by use of ethylene oxide as indicated in Table XI.

Referring to Table XI, in regard to Example 19G it will be noted again that the three oxides were used and 19G was obtained from 58F. Example 58F, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19G and subsequent examples, such as 20G, 21G, etc., propylene oxide was added.

Tables XII, XIII and XIV give the data in regard to the oxylalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table IX in greater detail, the data are as follows: The first column gives the example numbers,

such as 1E, 2E, 3D, etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1E through 6E, is Example 1D, although it would be just as proper to say that in the case of 3E the oxyalkylation-susceptible compound was 1E, and in the case of 3E the oxyalkylation-susceptible compound was 2E. Actually reference is to the parent derivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the polyepoxidederived condensate previously referred to in the text.

The fourth column shows the amount of ethylene ox ide in the mixture prior to the particular oxyethylation step. In the case of Example 1E there is no oxide used but it appears, of course, in 2E, 3E and 4E, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda. The quantity used is indicated.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the amount of oxyalkylationsusceptible compound which in this series is the polyepoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide, and column twelve for butylene oxide. For obvious reasons these can be ignored in the series 1E through 18E.

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the amount of solvent at the end of the oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the' end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere,'particularly in the patent literature.

Referring now to the second series of compounds in Table IX, to wit, Examples 19E through 36E, the situation is the same except that it is obvious the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table IX now carries data as to the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37E through 54E in Table IX, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data appears in column six as to butylene oxide present before the particular oxyalkylation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table X is in essence the data presented in exactly al runs using one if alkali at any point As previously pointed dures may conparticularly 2G, 36, etc.,

xides so there are no blanks as Such distillation also may remove f uncombined oxide, if present Table XI,

ointed out certain initi some instances two oxides, had to be sed as intermediates subsequently for It would be confusing to refer in too h the entire series, comparable to what has been As previously p Reference to solvent and amount 0 The products resulting from these proce use of propylene oxide and butylene oxide. Examples beginning with 1G show the use of all three 0 in the first step of each stage Where one oxide is missing. It is not believed any further explanation need be offered in regard to Table XI oxide only, or in duplicated when u further reaction.

much detail in these various tables for the reason that all pertinent data appears and the tables are essentially selfexplanatory.

and the alkali left from this step out, Tables XII, XIII and XIV give operating data in connection wit said in regard to Examples 1E through 6E.

tain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation.

traces or small amounts 0 and volatile under the conditions employed.

all

the

TABLE IX ethylene nm Omen. m h V. d X MW U0 Cm k BOMMO .w t SC t. LAW m W W 505050741826624084 O 9 Q&S 7 7 6 56m M vfl m m 4.94038 050mB%% mW- m 1 OnIuO 1122 11234 234 M t 0 V .L w yw k m E M M t S 0 0 500000055555555 t time 399999988388833 a Mew n 0 .1 t 0 t t S P afib m G O C ms B 1 M Os X r O P 0& b 3 7 4 E 2 5 7 c 55555500000055555555 55 00000055555. 55 5 CR 33333399999988888833 33 99999988888&33%%%3%%%%%%%%%%%% Sb 4 4 nm4hd 4 d 4 4 4 4 d nmcmnmnmam3mk ATLAMATQ A A 4 3 1111111111111111111 1111111MMIBBBIBBMMMMMMMMMMMMBBBBBB 5 55.050000005555555555550000005555 5 5 i 3 33339999998888883333339999998SS8%S%%%%3%%%%%%W%%%%%% first by the 5 49.2 coincide as shown in Solvent,

lbs.

, in turn, refers to The same situf the same two Catalyst,

This means that there are xide.

used are ethylene oxide 20 1e makes it plain that Inversely, Example 55F the data under Molal Ratio in regard and propylene oxide goes back to the 10 derived condensate 1b. This is obvious,

ame situation is involved except, of 15 takes into consideration the solvent from the previous step oxide is used first and this, again is per- Three columns only are blank, to wit,

Composition before EtO, PrO, B110, lbs.

lbs.

olumns in which data does not appear, g concerned with the use of butylene oxide.

lies in Examples such as 37F and subsequent oso, lbs.

e, because the figures 64.8 and Ex. No.

y fact that reference to Example 1F and also shows that ethylene oxide was present at In Table X the s course, propylene fectly apparent.

Example 73F and subsequent examples relate to the the same way except the two oxides appear, to wit oxide and propylene oxide.

only three c three bein Furthermore, it shows which oxide was used ver very first stage. Furthermore, for ease of comparison and also to be consistent,

to ethylene oxide original diepoxideof cours with the figures for 1E derived from 1D Table IX the three referring to butylene o ation app examples where the two oxides and butylene oxide, and the tab ethylene oxide was used first.

and subsequent examples show the use 0 oxides but with butylene oxide being used first as shown on the table.

Theo. mol. wt.

0000000000 0000000000000000000000000000000000000000000000000000%0000000000000000000000000 6 2 2 238888894444427277732109 7777777777773 3 8865 .WQWHWWWW%%W&M%MWW4WBW4&6749499718529655432494.93$0369513074 827%294QQAOWWHF W- WWHWUUWWWUMWWWW 1 1 1 7 1 1 1 1 1 1 9 4 7 7 & 0 1 1 1 2 0w 1 92 7 9024.01 om 4 & 7 1- 2 3 4-7 1 7 7 om 9 80178 1 1 5 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 HMU1N1MHW-2 BM1fl2231122 111 111111111 2 11 NRMIMBMNWMHHHUBWBMEWH BuO alkyl. scept.

PrO

to 0 alkyl.

Molal ratio M0 to oxyto 0 alkyl. suscept. suscept. su

compd. compd. compd.

S01- 1 vent, lbs.

4 44 4 4 443 3 90344444444444 4003 4 MMMMMMMMMMMBBBBBBBMiM11MlMlMlllBlBll11111111111111 lmm l wmmm Catalyst, lbs.

11111111111111111111111111111111111111111111111111111LLLLLLLLLLLLLLLLLLLLLLLL.LLLLLLLLLLLLL Composition at end lbs.

Oxides 505050 505 505555 5 257025987658754219777 00000000- vovfiu ufi uon .QwAnQuJLL-O. M2Q567M2M571245 wwfimw flmm EtO, lrO, B110,

TABLE X oso, lbs.

555555000005555555555555000 0055555555555-00000005555555555550000005555555 5 550 0 5 5555 333333999998888888333333999 998c000880o33333no999999008008883333339999998888883%3%339%9%%%8%8888 Solvent, lbs.

7 4-2 9 7 22696944444455505551111119 4 L 1223 11231111111111112222222%%%%%mmmmmmMMM-D m5 Oxides O, BuO, lbs.

Composition before m mmuufi assess n S 4144444 4 3 om3 3 3 4 44 4 14 3 3 I w u Ono. E E

TABLE XI Composition before Composition at end E Oxides Oxides I Molal ratio N o. 080, Geta- Sol- Cata- Sol- Theo. Ex. S0, lyst, vent, OSC, lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO, B110, lbs. lbs. lbs. 15120, HO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. s. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suscept. eompd. compd. compd.

14. 35 56. 0 28.0 1. 14. 35 14. 35 3. 5 56. 0 28. 0 1. 5 14. 35 15. 9 193. 0 77. 6 20, 070 14. 35 3. 5 56.0 28.0 1. 5 14. 35 14.35 7. 0 56.0 28.0 1. 5 14. 35 31. 8 193.0 77. 6 20, 770 14. 35 7. 0 56.0 28. 0 l. 5 14. 35 14. 35 14. 0 56. 0 28.0 1. 5 14. 35 63. 6 193. 0 77. 6 22, 170 14. 35 14. 0 56.0 28.0 1. 5 14. 35 14. 35 21. 0 56.0 28.0 1. 5 14. 35 95. 4 193. 0 77. 6 570 14.35 21.0 56. 0 28. 0 1. 5 14. 35 14.35 28.0 56. 0 28. 0 .1. 5 14.35 127. 2 193.0 77. 6 24, 970 14. 35 28. 0 56. 0 28. 0 1. 5 14. 35 14. 35 56. 0 56. 0 28. 0 1. 5 14. 35 254. 4 193. 0 77. 6 30, 570 14. 90 15.0 69.0 1. 5 14. 90 14. 90 3. 75 15. 0 60.0 1. 5 14. 90 17. 05 51. 7 166. 2 11, 920 14.90 3. 75 15.0 60.0 1. 5 14.90 14.90 7. 50 15.0 60.0 1. 5 14.90 34. 51. 7 166. 2 12,670 14. 90 7. 50 15. 0 60. 0 l. 5 14.90 14.90 15.0 15.0 60. 0 1. 5 14. 90 68. 2 51. 7 166.2 13, 170 14.90 15.0 15.0 60.0 1. 5 14. 90 14. 90 22. 5 15. 0 60. 0 1. 5 14.90 102. 3 51. 7 166.2 14, 670 14.90 22. 5 l5. 0 60.0 1. 5 14. 9O 14. 90 30. 0 15. 0 60. 0 1. 5 14.90 136. 4 51. 7 166. 2 16, 170 15. 90 30. 0 15.0 60.0 1. 5 14.90 14. 90 60. 0 15. 0 60. 0 1. 5 14.90 272. 8 51. 7 166. 2 22,170 13.85 60.75 54.0 2. 0 13.85 13.85 6. 75 60. 75 54. 0 2.0 13.85 30. 7 209. 15. 0 24, 370 13.85 6. 75 60. 75 54.0 2.0 13. 85 13.85 13. 60.75 54.0 2. 0 13.85 61. 4 209. 25 15.0 25, 720 13.85 13. 50 60.75 54. 0 2. 0 13.85 13.85 27.0 60.75 54. 0 2. 0 13.85 122. 8 209. 25 15. 0 27, 070 13. 85 27. 0 60. 75 54. 0 2. 0 13. 85 13. 85 40. 5 60. 75 54. 0 2. 0 13. 85 184. 2 209. 25 15. 0 29, 770 13.85 40. 5 60.75 54. 0 2.0 13. 85 13.85 54.0 60. 75 54. O 2.0 13.85 245. 6 209. 25 15.0 32, 470 13. 85 54. 0 60. 75 54. 0 2. 0 13. 85 13. 85 67. 5 60. 75 54. 0 2. 0 13. 85 307. 0 209. 25 15. 0 35, 170 14. 35 14.0 14.0 1. 5 14. 35 14. 35 14. 0 14. 0 14.0 1. 5 14. 35 63. 6 48. 25 38. 8 11,270 14.35 14.0 14.0 14. 0 1. 5 14. 35 14.35 14.0 21. 0 l4. 0 1. 5 14. 35 63. 6 62. 37 38. 8 12, 670 14.35 14.0 21. 0 14.0 1. 5 14.35 14.35 14.0 28. 0 14. O 1. 5 14. 35 63. 6 96. 5 38. 8 14,070 14. 35 14. 0 28. 0 14.0 1. 5 14.35 14.35 14.0 35.0 14.0 1. 5 14. 35 63. 6 120. 62 38. 8 15, 470 14. 35 14.0 35. 0 14.0 1. 5 14. 35 14. 35 14. 0 42. 0 14.0 1. 5 14. 35 63. 6 144. 75 38. 8 16, 870 14. 35 14. 0 42.0 14.0 1. 5 14. 35 14.35 14.0 49.0 14.0 1. 5 14. 35 63. 6 168. 87 38. 8 18, 270 14. 9 22.5 15.0 1. 5 14. 9 14.90 22.5 15.0 15.0 1. 5 14.90 102. 3 V 51.7 41. 6 13, 480 14. 9 22. 5 15. 0 15. 0 1. 5 14. 9 14. 90 22. 5 22. 5 15. 0 1. 5 14. 90 102. 3 77. 41. 6 14, 980 14. 9 22. 5 22. 5 15. 0 1. 5 14. 9 14. 90 22. 5 30. 0 l5. 0 1. 5 14. 90 102. 3 103. 4 41. 6 16, 480 14. 9 22. 5 30.0 15.0 1. 5 14. 9 14. 90 22. 5 37. 5 15. 0 1. 5 14. 90 102. 3 129. 25 41. 6 17, 980 14. 9 22. 5 37. 5 15. 0 1. 5 14. 9 14.90 22. 5 45.0 15.0 1. 5 14.90 102.3 155. 1 41. 6 19, 480 14. 9 22. 5 45. 0 15. 0 1. 5 14.9 14.90 22. 5 60.0 15. 0 1. 5 14. 90 102.3 206. 8 41. 6 22, 480 41. 4 41.4 27.0 1. 5 13.85 13.85 41. 4 13. 5 27. 0 1. 5 13.85 188. 4 46. 6 62. 5 18, 250 41. 4 41. 4 27.0 1. 5 13. 85 13. 85 41. 4 13. 5 27. 0 1. 5 13. 85 188.4 46. 6 62. 5 250 41. 4 41. 4 27. 0 1. 5 13. 85 13.85 41. 4 40. 5 27. 0 1. 5 13.85 188.4 139. 8 62. 5 23, 650 41. 4 41. 4 27.0 1. 5 13.85 13. 85 41. 4 47. 25 27. 0 1. 5 13. 85 188. 4 163. 1 62.5 000 41. 4 41. 4 27. 0 l. 5 13.85 13.85 41. 4 54. 0 27. 0 1. 5 13.85 188. 4 186. 4 62. 5 26, 350 41. 4 41. 4 27. 0 1. 5 13. 85 13. 85 41. 4 60. 27. 0 1. 5 13. 188. 4 209. 7 62.5 27, 700

Solubility Water Kerosene Insoluble. D

D0. Do. Do.

(10-. Insoluble ulslflable Soluble fin fin Soluble.-.

Soluble.

Do. Insoluble.

Do. Do. Disperslble. Soluble.

Do. Insoluble.

Do. Do. Dlsperslble. Soluble.

Soluble. Insoluble.

1.125 ule.

Do. Soluble.

TABLE XIII Max. Max. Solubility Ex. temp., pres., Time,

No. 0. p. s. i. hrs.

Water Xylene Kerosene Insoluble.

Do. Do. Do. Do.

Soluble.

Insoluble.

TABLE XIV Solubility Time.

8.1. hrs. 9 Water Kerosene Insoluble Insoluble.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i.e., no attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, amber and to a straw or light straw color. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color the product. Products can be prepared in which the final color is a lighter amber or straw color with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen atom, the removal of the alkaline catalyst is somewhat more diflicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

PART 9 As to the use of conventional demulsifying agents reference is made to US. Patent No. 2,626,929, dated Ianuary 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 59F, herein described.

PART 10 The products, compounds, or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-inoil type as described in detail in Part 9, preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is a somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure wherein R and R" are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 9, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 8, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and 

1. A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; AND (3) OXYALKYATION WITH AN ALPHA-BETA MONOEPOXIDE; SAID FIRST MANUFACTURING PROCESS BEING A STEP OF (A) CONDENSING (A) FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHNEOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLKOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID BEING OF THE FORMULA 